Processes using solid-acid catalyst compositions

ABSTRACT

New catalyst compositions comprise sulfated and calcined mixtures of (1) a support comprising an oxide or hydroxide of a Group IV-A element, (2) an oxide or hydroxide of a Group VI, VII or VIII metal, (3) an oxide or hydroxide of a Group I-B, II-B, III-A, III-B, IV-B, V-A or VI-A metal and (4) a metal of the Lanthanide Series of the Periodic Table. A process for alkylation of acyclic saturated compounds with acyclic unsaturated compounds utilizing such catalyst compositions.

This is a divisional of copending application Ser. No. 07/800,796 filedon Nov. 27, 1991, now U.S. Pat. No. 5,214,017.

The reaction of isobutane with low (C₂ -C₅)molecular weight olefins toproduce C₆ -C₉ paraffins is commonly referred to as alkylation. Incommercial practice this reaction is carried out in the presence of acidtype catalysts such as concentrated sulfuric acid or HF. The reaction isan important process in the petroleum industry as it represents a meansto upgrade chemical compounds in crude oil for which there may be littlevalue to high octane fuel components. The two acids mentioned above arethe catalysts of choice as the process is now operated commercially, buteach of them while producing a satisfactory alkylate for fuel blendinghas serious drawbacks. The use of HF presents a significant ecologicalhazard should it escape into the atmosphere, and the sulfuric acidprocess is very corrosive and energy consuming as it needs to beoperated at below ambient temperatures in order to provide asatisfactory alkylate. Certain solid compositions with acidic propertieshave been found to catalyze this reaction as disclosed in the followingJapanese patents.

In Hatakeyama et al Japanese Kokai Patent, SHO 61-183230, Aug. 15, 1986,fractions rich in 2,2,3-trimethylpentane are produced from butenes andisobutane by alkylation over a super strongly acidic zirconia catalystobtained by contacting zirconium hydroxide or zirconium oxide with asolution containing sulfate radical, followed by roasting.

In Abstract No. 106: 216817b, CA Selects: Catalysis (Applied & PhysicalAspects), Issue 13, Jun. 29, 1987, Ito et al, Jpn. Kokai Tokkyo Koho JP61,242,641 (86,242,641), Oct. 28, 1986 is abstracted, disclosingcatalysts for isobutane alkylation prepared by impregnating sulfate ionor its precursor-containing materials and rare earth metals or theircompounds, e.g. lanthanum nitrate, on supports consisting of Group IVAor IVB metal hydroxides or oxides, followed by calcination andstabilization.

In the corresponding Ito et al Japanese Kokai Patent, SHO 61-242641,Oct. 28, 1986, application SHO 60-84515 filed Apr. 22, 1985, a solidacidic catalyst for alkylation of isoparaffin with olefin is disclosed.The catalyst is obtained by adding a rare earth element or itscompounds, and sulfate radical or its precursor to a supporting membermade of hydroxide or oxide of Group IV metals, followed by sintering at400°-800° C,. for stabilization. Hydroxide or oxide of at least one typeof metals chosen from titanium, zirconium, hafnium, silicon, germaniumand tin is used; particularly hydroxide or oxide of zirconium ortitanium is preferred. Tantalum and cerium or their compounds aredisclosed, as most desirable rare earths; praseodymium, neodymium,samarium and gadolinium are also disclosed.

In Hosoi et al Japanese Kokai Patent, HEI 1-245853 disclosure date Oct.2, 1989, Application No. SHO 63-73409, Mar. 29, 1988, solid acidcatalyst for alkylation is provided, using at least one type of metalcontaining metals of Group II-b, for example zinc or mercury, Group V-a,for example vanadium, niobium or tantalum, Group VI-a, for examplechromium, molybdenum or tungsten, Group VII-a, for example manganese orrhenium, on a carrier consisting of oxides or hydroxides with Group IIIand/or Group IV metal hydroxides or its compounds and a sulfate radicalor precursors of a sulfate radical. Sulfated zinc/zirconium hydroxides,chromium/zirconium hydroxides, vanadium/zirconium hydroxides,manganese/zirconium hydroxides, zinc/titanium hydroxides,zirconium/titanium hydroxides, zirconium/aluminum hydroxides aredisclosed.

In Shimizu et al Japanese Kokai Patent HEI 1-245854, disclosure dateOct. 2, 1989, Application No. SHO 63-73410, Mar. 29, 1988, a solid acidcatalyst for alkylation of isobutane by olefins is obtained by adding asulfate or precursor thereof to a carrier comprising compound metalhydroxides or compound metal oxides of at least more than two kinds ofmetals selected from titanium, zirconium, silicon and tin. Sulfatedzirconia/titania, zirconia/tin oxide, zirconium/silicon catalysts aredisclosed.

Chemical Week, Nov. 25, 1987, on page 28, discloses superacids obtainedby sulfating zirconium, titanium and iron oxides, s catalysts foralkylation of ortho-xylene by styrene.

We have discovered that certain metal combinations when incorporatedwith the strongly acidic solid-acids, which are in one embodiment of theinvention generated by treating zirconia with ammonium sulfate and thencalcining at high temperatures, provide alkylation catalysts superior tothat obtained by the use of the sulfated zirconia alone. That is to saythat the alkylate produced by the modified sulfated zirconia has ahigher proportion of 8-carbon compounds than that obtained when usingonly the sulfated zirconia. Concurrently the amount of light ends (5-7carbon products) which arise from cracking the C-8 and higher fractionsis reduced. Additionally the alkylation reaction can be carried out atroom temperature to provide good yields of alkylate, thus eliminatingthe need for sub-ambient cooling and results in a more energy efficientoperation. Furthermore these new catalysts provide a significantlyhigher percentage of the high octane trimethylpentanes within the8-carbon fraction than one obtains with sulfated zirconia alone or withthe traditional acid catalysts.

The new composition of matter according to the invention comprises asulfated and calcined mixture of (1) a support comprising an oxide orhydroxide of a Group IV-A element, (2) an oxide or hydroxide of a firstmetal selected from the group consisting of Group VI, Group VII or GroupVIII metal, (3) an oxide or hydroxide of a second metal selected fromthe group consisting of Group I-B, Group II-B, Group III-A, Group III-B,IV-B, V-A or VI-A metal and (4) an oxide or hydroxide of a third metalselected from the group consisting of metals of the Lanthanide Series ofthe Periodic Table.

The solid super-acid catalyst is prepared by incorporating the desiredmetals (or ions) onto a sulfated zirconia support or other supportcomprising an oxide or hydroxide of a Group IV-A element, by techniquesknown to those skilled in the art of catalyst preparation, for example,the technique disclosed in Example 1 of U.S. Pat. No. 4,918,041 supra,wherein a composite of zirconia, iron and maganese is prepared, calcinedand sulfated. Alkylate superior to that obtained by employing the solidsuper-acid support alone is realized when a catalyst containing threemetals or metal ions is used if one of the metals (or metal ions)employed is molybdenum or another Group VI to Group VIII metal, a secondmetal comes from Groups V-A (V, Nb, Ta), VI-A (Cr, Mo, W), I-B (Cu, Ag,Au), II-B (Zn, Cd, Hg), III-A (Sc, Y), III-B (B, Al, Ga, In, Tl), IV-B(Ge, Sn, Pb), and a third metal from the Lanthanide Series of the IUPACPeriodic Table. The second metal is different from the first, thougheach may be from the same group of the Periodic Table. Metals from theLanthanide Series which may be used are cerium, lanthanum, neodymium,praseodymium, samarium, gadolinium, and dysprosium of which cerium andlanthanum are preferred.

In one embodiment of the invention, the first metal is a metal fromGroup VI, VII or VIII, for example molybdenum, and the second metal is adifferent metal from Group VI, VII or VIII, for example tungsten.

Typical alkylation results are illustrated in Table I wherein it isrecorded that the catalyst compositions of this invention provide higherconcentrations of 8-carbon containing species and lower amounts of C₅-C₇ cracked products than does a catalyst prepared from the super-acidzirconia support alone, or from using the traditional acid catalysts.

The data in Tables I & II were obtained from a semi-batch laboratoryreactor operated as described below, but it is believed that theadvantage provided by the catalysts of this invention can be obtained inother commercially appropriate reactor configurations. A small (300 ml)Parr reactor was charged with 20 gms. of dry catalyst and 50 mls. ofisobutane. With stirring, a 15/1 feed of isobutane/butene-2 was added atthe rate of 43 mls./hr for four hours. At the end of the addition thereactor was allowed to stir an additional hour. The product waswithdrawn and analyzed by gas chromatography to determine the carbonnumber and isomer distributions which are reported in the tables.

The support upon which the metal is incorporated in this embodiment neednot be entirely composed of sulfated zirconia. Mixtures of zirconia withother appropriate oxides such as the oxides from elements in GroupsIII-A & B, IV-A & B of the Periodic Table may be used. Mixtures of theseoxides along with zirconia will, upon being impregnated with theappropriate metals and sulfated, provide superior solid-acid alkylationcatalysts. For example, silica-zirconia, titania-zirconia,aluminazirconia, hafnia-zirconia represent appropriate supports forsulfation and impregnation within the scope of this disclosure.Alternatively, other elements from Group IV-A may be used instead ofzirconium.

                  TABLE I                                                         ______________________________________                                        ALKYLATE COMPOSITION                                                                 RUN NUMBER                                                                    1         2         3                                                         H.sub.2 SO.sub.4                                                                        ZrO.sub.2 /SO.sub.4                                                                     Mo/W/Ce                                            ______________________________________                                        C-3      0.00        0.34      0.42                                           C-5      5.17        34.79     5.83                                           C-6      5.37        11.30     3.03                                           C-7      5.26        9.14      6.10                                           C-8      66.36       37.66     77.83                                          C-9      4.73        5.72      1.72                                           C-10     1.83        0.58      1.42                                           C-12     5.24        0.47      3.44                                           C->12    0.01        0.00      0.14                                           ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        ALKYLATE ISOMER DISTRIBUTION                                                             RUN NUMBER                                                                            1         2                                                           H2SO4   ZrO2/SO4  Mo/W/Ce                                          ______________________________________                                        2-MeC4       5.726     34.704    5.856                                        OTHER C5     0.010     0.222     0.000                                        TOTAL C5     5.737     34.926    5.856                                        2,2-DMeC4    0.001     3.715     0.130                                        2,3-DMeC4    5.455     2.384     1.603                                        2-MeC5       0.000     3.651     0.874                                        3-MeC5       0.548     1.497     0.440                                        TOTAL C6     6.004     11.248    3.047                                        2,2-DMeC5    0.000     1.248     0.072                                        2,4-DMeC5    3.162     4.020     3.935                                        2,2,3-TMeC4  0.246     0.213     0.094                                        3,3-DMeC5    0.000     0.915     0.181                                        3-MeC6       0.154     0.721     0.188                                        2,3-DMeC5    1.813     1.553     1.487                                        3-EtC5       0.148     0.508     0.166                                        OTHER C7     0.000     0.074     0.000                                        TOTAL C7     5.523     9.251     6.123                                        2,2,4-TMeC5  27.420    17.440    36.404                                       2,2-DMeC6    0.011     0.896     0.217                                        2,5-DMeC6    4.405     1.488     1.069                                        2,4-DMeC6    2.855     1.220     0.000                                        2,2,3-TMeC5  1.139     5.767     9.184                                        3,3-DMeC6    0.000     0.351     0.087                                        2,3,4-TMeC5  16.073    3.771     14.195                                       2,3,3,-TMeC5 15.794    5.712     13.437                                       2,3-DMeC6    2.943     0.582     1.061                                        3-Et-2-MeC5  0.091     0.037     0.065                                        3-MeC7       0.057     0.148     0.051                                        3,4-DMeC6    0.518     0.148     0.282                                        4-MeC7       0.050     0.129     0.051                                        3-Et-3-MeC5  0.002     0.000     0.094                                        OTHER C8     0.020     0.037     0.029                                        TOTAL C8     71.381    37.726    76.224                                       2,2,5-TMeC6  2.574     3.604     1.747                                        OTHER C9     1.462     1.922     1.776                                        TOTAL C9     4.036     5.527     3.523                                        TOTAL C10    1.714     0.582     1.430                                        TOTAL C12    5.226     0.471     3.458                                        TOTAL > C12  0.364     0.000     0.144                                        SUM (AREA %) 99.984    99.732    99.805                                       CALC RES OCT 93.50     92.33     99.378                                       ______________________________________                                    

In Run 2, the amount of C5, C₆ and C₇ isomers produced is considerablyreduced from that obtained in Run 1. The quantity of C₈ alkylate isgreater in Run 2 than in Run 1 or in the run with H₂ SO₄. The quantityof trimethylpentanes (i.e., the high octane isomers) in the C₈ fractionof Run 2 is greater than that in Run 1 or in the run with H₂ SO₄. Thequantity of C₉ containing fractions is reduced in Run 2 vs. Run 1 andthe run with H₂ SO₄.

All of the above combine to result in a very significant increase in thecalculated Research Octane of the product of Run 2 (99.4) vs the productof Run 1 (92.3) or the product obtained with H₂ SO₄ (93.5.).

The invention claimed is:
 1. In a process for catalytic reaction of anacyclic saturated compound having 2 to 10 carbon atoms per molecule withan acyclic unsaturated compound having 2 to 5 carbon atoms per moleculeto form compounds having greater molecular weight than the startingmaterials, the improvement which comprises utilizing as catalyst forsuch reaction a sulfated and calcined mixture of (1) a supportcomprising an oxide or hydroxide of a Group IV-A element, (2) an oxideor hydroxide of a first metal selected from the group consisting of aGroup VI, Group VII or Group VIII metal, (3) a second metal selectedfrom the group consisting of a Group I-B, II-B, III-A, III-B, IV-B, V-Aor VI-A metal and (4) a third metal selected from the group consistingof the metals of the Lanthanide Series of the IUPAC Periodic Table. 2.Process according to claim 1 wherein said first metal is molybdenum. 3.Process according to claim 1 wherein said second metal is vanadium,niobium or tantalum.
 4. Process according to claim 1 wherein said secondmetal is chromium, molybdenum or tungsten.
 5. Process according to claim1 wherein said second metal is copper, gold or silver.
 6. Processaccording to claim 1 wherein said second metal is zinc, cadmium ormercury.
 7. Process according to claim 1 wherein said second metal isscandium or yttrium.
 8. Process according to claim 1 wherein said secondmetal is boron, aluminum, gallium, indium or thallium.
 9. Processaccording to claim 1 wherein said second metal is germanium, tin orlead.
 10. Process according to claim 1 wherein said third metal iscerium, lanthanum, neodymium, praseodymium, samarium, gadolinium ordysprosium.